EP0044540B1 - Compositions d'organopolysiloxanes pour le traitement de matières textiles; leur préparation, un procédé pour le traitement de matières textiles et matières textiles ainsi traitées - Google Patents

Compositions d'organopolysiloxanes pour le traitement de matières textiles; leur préparation, un procédé pour le traitement de matières textiles et matières textiles ainsi traitées Download PDF

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EP0044540B1
EP0044540B1 EP81105625A EP81105625A EP0044540B1 EP 0044540 B1 EP0044540 B1 EP 0044540B1 EP 81105625 A EP81105625 A EP 81105625A EP 81105625 A EP81105625 A EP 81105625A EP 0044540 B1 EP0044540 B1 EP 0044540B1
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radical
group
radicals
formula
carbon atoms
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EP0044540A2 (fr
EP0044540A3 (en
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Eugene Ray Martin
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Wacker Chemical Corp
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Wacker Chemical Corp
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature

Definitions

  • the present invention relates to silicone polymers, particularly to a composition obtained from silylated polyethers and silanol terminated polysiloxanes and more particularly to a process for coating textile materials with the silicone polymers.
  • silicone polymers can be dispersed in water to form stable emulsions or solutions. Separate emulsions consisting of a crosslinker and a catalyst are not required to effect curing of the compositions of this invention. Moreover, the compositions of this invention provide a finish for textile substrates that do not have a limited stability.
  • composition containing silicone polymers Another object of this invention is to provide a composition containing silicone polymers which may be applied to textile materials to impart a soft, silky hand thereto. Still another object of this invention is to provide a composition containing silylated polyethers and silanol terminated organopolysiloxanes. A further object of this invention is to provide a composition which is obtained from the reaction of silylated polyethers and silanol terminated organopolysiloxanes. A still further object of this invention is to provide a stable emulsion which does not require additives for effecting treatment of textile materials.
  • compositions containing silylated polyethers and silanol terminated organopolysiloxanes may be combined with water to form dispersions which may be used to treat textile substrates to impart a soft, silky and durable hand thereto.
  • the silylated polyethers which are mixed with the silanol terminated organopolysiloxanes may be represented by the formula wherein at least one R is selected from the group consisting of an -NH radical, an ammonium radical or a radical of the formula in which the radicals represented by R are linked to the polyether through an ester, amine, amide or ammonium radical and the remaining R groups are selected from hydrocarbonoxy radicals having up to 18 carbon atoms, hydroxyl radicals or a radical of the formula
  • Suitable examples of hydrocarbonoxy radicals represented by R having from 1 to 18 carbon atoms are methoxy, ethoxy, propoxy, butoxy, octoxy, dodecoxy and octadecoxy radicals.
  • suitable radicals represented by R 1 are divalent hydrocarbon radicals having from 1 to 10 carbon atoms such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene and decamethylene radicals.
  • Examples of divalent cyclic radicals represented by R 1 are phenylene, naphthenylene, cyclohexylene and cyclohexenylene radicals.
  • Suitable examples of monovalent hydrocarbon radicals represented by R and R 3 are alkyl radicals, e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl and octadecyl radicals; aryl radicals, e.g., the phenyl radical; alkaryl radicals, e.g., tolyl, xylyl and ethylphenyl radicals; cycloalkyl radicals, e.g., cyclobutyl, cyclohexyl, cyclodecyl radicals; aralkyl radicals, e.g., benzyl, 2-phenylethyl and 2-phenylpropyl radicals.
  • alkyl radicals e.g., methyl, ethyl, propyl, butyl, hexyl, octyl,
  • Examples of preferred divalent hydrocarbon radicals represented by R 5 are radicals having up to 50 carbon atoms, of the formula where m is from 0 to 24, n is 2, 3 or 4 and z is a number of from 1 to 10.
  • suitable divalent radicals represented by R 6 are hydrocarbon radicals having preferably up to 10 carbon atoms such as ethylene, trimethylene, hexamethylene and octamethylene radicals and hydrocarbonoxy containing radicals having up to 50 carbon atoms of the formula where r is from 1 to 24, and z is the same as above.
  • hydrocarbonoxy containing radicals are ethylene oxide, trimethylene oxide, tetramethylene oxide and alkenylene radicals having preferably up to 10 carbon atoms such as vinylene, propenylene, butenylene and hexenylene.
  • the silylated polyethers of this invention may be prepared by several different techniques. Some of the techniques for preparing these silylated polyethers are described in EP 0026366 A 1. (Priority: 9-10-79, US 74 188).
  • One method for preparing the silylated polyethers is to react oxyalkylene glycols or copolymers thereof with a cyclic anhydride at a temperature of from 80° to 185°C to form a half ester which is then reacted with an aminofunctional silane having at least 1 and up to 3 alkoxy groups per silicon atom at from 0° to 110°C.
  • Another method for preparing the silylated polyethers is to react an aminofunctional silane with a cyclic anhydride at a temperature of from 25° to 110°C thus forming a carboxylic acid functional silane, and thereafter reacting the resultant silane with an amine terminated oxyalkylene polymer or copolymers thereof at a temperature of from 0° to 110°C.
  • silylated polyethers wherein R is an ammonium ion and A is a group of the formula or of the formula can be prepared.
  • the resultant product is an ammonium salt.
  • the reactants are heated at temperatures above 115°C.
  • Still another method for preparing the silylated polyethers is to react an amine terminated oxyalkylene polymer or copolymers thereof with a cyclic anhydride to form a carboxylic acid functional polymer which is then reacted with an aminofunctional silane at a temperature of from 0° to 100°C.
  • the silylated polyethers employed in this invention may be prepared by reacting an oxyalkylene glycol or copolymers thereof with a cyclic anhydride and thereafter reacting the resultant carboxylic acid polymer with a haloalkylalkoxysilane in the presence of triethylamine at a temperature of from 80° to 150°C.
  • the silylated polyethers may also be prepared by reacting an amine terminated oxyalkylene polymer or copolymers thereof with a haloalkylalkoxysilane and thereafter reacting the resultant product with a sodium alkoxide at a temperature of from about 80° to 150°C.
  • silylated polyethers used in the compositions of this invention may also be prepared by substituting dicarboxylic acids having up to 10 carbon atoms for the anhydrides described above.
  • esterification catalysts such as titanates, alkali metal hydroxides or mineral acids.
  • dicarboxylic acids which may be used are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • glycols and copolymers thereof which are used to make the silylated polyethers which are employed in the compositions of this invention are well known in the art. These glycols and coplymers thereof may be illustrated by the following formula: where G is hydrogen or an alkyl radical having from 1 to 18 carbon atoms, in which at least one G must be hydrogen, a is a number of from 0 to 4, n is 2, 3 or 4, x is a number of at least 1 and up to 600, preferably from 10 to 250.
  • these glycols are made by the homopolymerization or copolymerization of ethylene oxide, propylene oxide and/or butylene oxide using various alcohols as initiators. Examples of alcohols are glycerine, methanol, ethylene glycol, ethanol and t-butanol.
  • Suitable examples of anhydrides that may be used to make the silylated polyethers which are employed in compositions of this invention are succinic anhydride, glutaconic anhydride, maleic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, 3-cyclohexene-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 1,8-naphthalic anhydride and phthalic anhydride.
  • aminofunctional silanes which may be used to prepare the silylated polyethers which are employed in the compositions of this invention are beta-aminopropyltriethoxysilane, gamma- aminopropyltrimethoxysilane, methyl-beta-(aminoethyl)-gamma-aminopropyldimethoxysilane, omega- aminohexyltributoxysilane, beta-(aminoethoxy)propyltrimethoxysilane, beta-(aminoethoxy)hexyltri- ethoxysilane, beta-(aminopropoxy)butyltributoxysilane, and
  • Examples of amine terminated oxyalkylene homopolymers and copolymers which may be used to prepare the silylated polyethers which are employed in the compositions of this invention are those having the general formula wherein a, n and x are the same as above. These polymers can be synthesized by effecting the amination of the corresponding oxyalkylene homopolymer or copolymer having terminal haloalkyl groups. These haloalkyl terminated polymers may be prepared by reacting oxyalkylene glycol or copolymers thereof with a phosphorous trihalide.
  • Suitable examples of divalent hydrocarbon radicals represented by R 7 are ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, dodecamethylene, hexadecamethylene and octadeca- methylene radicals.
  • haloalkylsilanes that may be used are chloropropyltrimethoxysilane, chloropropylmethyldimethoxysilane, chloropropyldimethylethoxysilane, bromopropyl- triethoxysilane, iodobutylmethyldimethoxysilane and bromobutylethyldimethoxysilane.
  • the mole ratio of anhydride to amine or hydroxyl groups linked to the polyether or silane may be varied over a wide range.
  • the mole ratio of anhydride to amine or hydroxyl group may range from 0.17:1 to 1.25:1 with the preferred ratio of anhydride to amine or hydroxyl groups being from 0.33:1 to 1.1:1, with the proviso that at least one amine or hydroxyl group per molecule is reacted with the anhydride.
  • the mole ratio of the carboxylic acid radical formed from the reaction of the cyclic anhydride with the above amine or hydroxyl groups, to the haloalkyl radicals linked to the silane or the amine groups linked to the silane or polyether may range from 0.17:1 to 1.25:1 with the proviso that at least one carboxylic acid radical per molecule is present for each amine group in order that an ammonium salt or the corresponding amide or the ester is formed.
  • Branched or linear silanol terminated organopolysiloxanes having structural units of the formula are mixed with the silylated polyethers to form the silicone polymer compositions of this invention, in which R 3 is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms and w is 2, 3 or 4. All unsatisfied valences of the silicon atoms are satisfied through Si-O-Si linkages or hydroxyl groups.
  • the organopolysiloxanes have a viscosity of from 15 to 1,000,000 mm 2 /s (cs.) at 25°C and more preferably from 25 to 500,000 mm 2 /s (cs.) at 25°C.
  • Emulsions of the silanol terminated organopolysiloxanes may also be used.
  • Suitable examples of monovalent hydrocarbon radicals are alkyl radicals such as methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl and octadecyl radicals; cycloalkyl radicals such as cyclohexyl, cyclobutyl, cyclodecyl radicals; aryl radicals such as the phenyl radical; aralkyl radicals such as benzyl, 2-phenylethyl, and the 2-phenylpropyl radical and alkaryl radicals such as tolyl, xylyl and ethylphenyl radicals.
  • compositions of this invention may be prepared by mixing the silylated polyether with the silanol terminated organopolysiloxane in the absence of or presence of certain diluents, such as solvents and emulsifiers, preferably at an elevated temperature, e.g. up to about 90°C and above.
  • suitable solvents include water, hydrocarbon solvents such as heptane or di-n-butylether, aromatic hydrocarbons, or chlorinated hydrocarbons.
  • emulsifiers examples include non-ionic emulsifiers such as nonylphenol ethylene oxide adducts, polyoxyethylene stearates, etc; anionic emulsifiers such as sodium lauryl sulfate, sodium stearate, etc; cationic emulsifiers such as quaternary chlorides, etc., or amphoteric emulsifiers such as aminoacids, etc.
  • the preferred method for preparing the compositions containing silicone polymers is to mix the silylated polyether and the silanol terminated polysiloxane in the absence of a diluent at a temperature of from 25° to 70°C.
  • the resultant composition can then be mixed with diluents in an amount of from 0.25 to 99.75 parts of the composition containing silicone polymers with from 99.75 to 0.25 part of diluent and more specifically, from 0.5 to 50 parts of the composition containing silicone polymers with from 99.5 to 50 parts of diluent.
  • Dispersions can be made by vigorously mixing water as a diluent with the composition containing silicone polymers for about 1 hour at room temperature.
  • the silicone polymer compositions of this invention include mixtures of silylated polyethers and silanol terminated polysiloxanes, reaction products of silylated polyethers and silanol terminated polysiloxanes and various mixtures of the above. These polymers may be prepared by employing an excess of either the silyated polyether or the silanol terminated polysiloxane.
  • the amount of silylated polyether present in the compositions of this invention may range from about 0.25 to 99.75 percent by weight and the amount of silanol terminated organopolysiloxane may range from about 99.75 to 0.25 percent by weight based on the weight of silylated polyether and silanol terminated organopolysiloxane.
  • the weight ratio of silylated polyether to silanol terminated organopolysiloxane may range from 1 to 99 percent to 99 to 1 percent by weight and more preferably in a weight ratio of from 95 to 50 percent to 5 to 50 percent of silylated polyether to silanol terminated organopolysiloxane based on the combined weight of the silylated polyether and silanol terminated organopolysiloxane.
  • compositions of this invention containing silylated polyethers and silanol terminated organopolysiloxanes can be applied to textile materials in admixture with other substances which have been used heretofore to impart certain properties to textile materials.
  • Other substances which may be used in combination with the compositions of this invention are lubricating agents, agents which improve abrasion resistance of the treated fibers, materials which improve the fragrance of the treated materials, antistatic lubricants, fabric softeners, fire retardants, soil resistant materials and crease-proofing agents.
  • crease-proofing agents are aminoplast resins such as urea-formaldehyde resins, malamine- formaldehyde resins, and dimethylol dihydroxy ethylene urea which may contain magnesium chloride and zinc nitrate as catalysts. In certain applications the amount of crease-proofing agent may be reduced when using the compositions of this invention without sacrificing crease-proofing properties.
  • Other crease-proofing resins are phenol-formaldehyde resins and hydroxyethyl methacrylate resins.
  • compositions of this invention may be applied in concentrated form or preferably dispersed in water or in organic solvents such as di-n-butylether, aliphatic hydrocarbons, aromatic hydrocarbons, and/ or chlorinated hydrocarbons and then applied.
  • organic solvents such as di-n-butylether, aliphatic hydrocarbons, aromatic hydrocarbons, and/ or chlorinated hydrocarbons and then applied.
  • the stability of water dispersions of the compositions of this invention may also be enhanced by the addition of certain emulsifiers.
  • stabilizing agents include non-ionic emulsifiers such as nonylphenol ethylene oxide adducts, polyoxyethylene stearates, etc.; anionic emulsifiers such as sodium lauryl sulfate, sodium stearate, etc.; cationic emulsifiers such as quaternary ammonium chlorides, etc.; or amphoteric emulsifiers such as amino acids, etc.
  • compositions of this invention may be applied to all textile materials, preferably organic textile materials on which organopolysiloxanes have been or could have been applied heretofore.
  • textile materials preferably wool, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose acetate, polyacrylonitrile fibers, and mixtures of such fibers.
  • the textile materials may consist of staple or monofilament fibers.
  • compositions of this invention and other substances may be applied to the textile materials by any means known in the art, such as by spraying, immersion, foaming, padding, calendering or by gliding the fibers across a base which has been saturated with the compositions of this invention.
  • the solids add-on is in the range of from 0.025 to 20 percent and preferably from about 0.04 to 10 percent, based on the weight of the original textile material.
  • the textile material After the textile material has been treated, it is dried at an elevated temperature, e.g., from about 50 to 200°C for a brief period of time, e.g., from about 3 to 15 minutes.
  • an elevated temperature e.g., from about 50 to 200°C for a brief period of time, e.g., from about 3 to 15 minutes.
  • the treated textile material should contain from about 0.025 to about 10 percent by weight on a dry basis of the cured composition of this invention.
  • Textile materials treated with the compositions of this invention possess beneficial properties such as a soft, durable hand and either hydrophobic or hydrophilic characteristics depending on the type of silicone polymer employed.
  • a carboxylic acid functional polymer is prepared by mixing about 2.000 parts (0.35 mole) of an oxyethyleneoxypropylene triol copolymer having a mole ratio of oxyethylene units to oxypropylene units of about 2.5 to 1 and a molecular weight of about 5,660 with about 106.1 parts (1.06 moles) of succinic anhydride and the resultant mixture is heated at about 175°C for eighteen hours.
  • the resultant product has a viscosity of 4,168 mm 2 /s (cs.) at 25°C.
  • Nuclear Magnetic Resonance analysis shows a mole ratio of the functional groups as follows:
  • the acid content is found to be about 0.58 milliequivalent of acid per gram while the theoretical value is 0.5 milliequivalent per gram.
  • the product is represented by the formula
  • silylated polyether which is a dark straw colored liquid and has a viscosity of about 24,460 mm 2 /s (cs.) at 25°C, may be represented by the formula
  • composition prepared in ⁇ Example 1 (c) are dispersed in 200 parts of water by mixing at room temperature for one hour.
  • the dispersion is an opaque, yellow, homogenous liquid with a viscosity of 57.5 mm 2 /s (cs.) at 25°C.
  • a rubber-like film is formed upon evaporation of the water.
  • silylated polyether prepared in Example 1(b) above are mixed with 100 parts of a silanol terminated-dimethylpolysiloxane, having a silanol content of about 2.5 percent and a viscosity of about 70 mm 2 /s (cs.) at 25°C, at a temperature of 25°C for 3 hours.
  • the resultant composition is an opaque, yellow liquid having a viscosity of about 57,500 mm 2 /s (cs.) at 25°C.
  • this composition About 100 parts of this composition are mixed with 200 parts of water at room temperature for 1 hour.
  • the dispersion is an opaque, white liquid having a viscosity of 25 mm 2 /s (cs.) at 25°C.
  • a rubber-like film is formed when the water is removed by evaporation.
  • Example 285 parts of the silylated polyether prepared in Example 1 (b) above are mixed at 70°C with 15 parts of a silanol terminated dimethylpolysiloxane having a silanol content of about 2.5 percent and a viscosity of about 70 mm 2 /s (cs.) at 25°C for 3 hours.
  • the resultant composition is an opaque, yellow liquid with a viscosity of 79,000 mm 2 /s (cs.) at 25°C.
  • this composition About 100 parts of this composition are mixed with 200 parts of water at room temperature for 1 hour.
  • the dispersion is an opaque, yellow liquid having a viscosity of 44.8 mm 2 /s (cs.) at 25°C.
  • a rubber-like film is formed upon evaporation of the water.
  • This composition About 100 parts of this composition are dispersed in 200 parts of water by mixing at room temperature for 1 hour.
  • the Dispersion is an opaque, yellow liquid with a viscosity of about 40 mm 2 /s (cs.) at 25°C.
  • a rubber-like film is formed upon evaporation of the water.
  • this composition About 100 parts of this composition are dispersed in 200 parts of water by mixing at room temperature for 1 hour.
  • the dispersion is an opaque, yellow liquid with a viscosity of about 50 mm 2 /s (cs.) at 25°C.
  • a sponge-like material is formed upon evaporation of the water.
  • Example 1 (b) About 135 parts of the silylated polyether prepared in Example 1 (b) above are mixed at 25°C with 15 parts of a silanol terminated dimethylpolysiloxane having a viscosity of 24 mm 2 /s (cs.) at 25°C and a hydroxyl content of 5.7 percent for 3 hours.
  • the resultant composition is an opaque, yellow liquid with a viscosity of 8,800 mm 2 /s (cs.) at 25°C.
  • this composition About 100 parts of this composition are dispersed in 200 parts of water by mixing at room temperature for 1 hour.
  • the dispersion is an opaque, white liquid with a viscosity of 23 mm l /s (cs.) at 25°C.
  • a rubber-like foam is formed upon evaporation of the water.
  • compositions About 100 parts of this composition are dispersed in 200 parts of water by mixing at room temperature for 1 hour.
  • the dispersion is an opaque, white liquid having a viscosity of about 30 mm 2 /s (cs.) at 25°C.
  • Example 1 (b) About 135 parts of the silylated polyether prepared in Example 1 (b) above are mixed with 15 parts of a silanol terminated dimethylpolysiloxane, having an OH content of about 3.8 percent and a viscosity of about 30 mm 2 /s (cs.) at 25°C, at a temperature of 70°C for 3 hours.
  • the resultant composition is an opaque, white, viscous liquid which by NMR analysis contains the following groups in the indicated ratios:
  • Example 1 (b) About 135 parts of the silylated polyether prepared in Example 1 (b) above are mixed with 15 parts of a silanol terminated dimethylpolysiloxane having a hydroxyl content of about 2.9 percent and a viscosity of about 30 mm 2 /s (cs.) at 25°C, at a temperature of 25°C for 3 hours.
  • the resultant composition is an opaque, yellow liquid with a viscosity of 16,400 mm 2 /s (cs.) at 25°C which by NMR analysis contains the following groups in the indicated ratios:
  • composition About 100 parts of this composition are mixed with 200 parts of water for 1 hour at room temperature.
  • the resultant composition is an opaque, white liquid having a viscosity of 30 mm 2 /s (cs.) at 25°C.
  • a rubber-like foam is obtained when the water is removed by evaporation.
  • Example 13 The procedure of Example 13 is repeated, except that the carboxylic acid functional polyether is prepared by substituting 58.8 parts of maleic anhydride containing 0.2 parts para-methoxyphenol for the phthalic anhydride.
  • the resultant composition prepared from the silylated polyether and silanol terminated dimethylpolysiloxane has a viscosity of 137,600 mm 2 /s (cs.) at 25°C.
  • a water solution of the silylated polyether prepared in Example 1 (b) above is prepared by mixing 100 parts of the silylated polyether with 200 parts water for 1 hour at room temperature.
  • aqueous emulsion containing 35 percent by weight of a silanol terminated dimethylpolysiloxane having a viscosity of about 70 mm 2 /s (cs.) at 25°C for 3 hours at a temperature of 70°C.
  • the resulting dispersion is an opaque, yellow liquid having a viscosity of 54 mm 2 /s (cs.) at 25°C.
  • the stability of the water dispersions containing 33 percent by weight of the compositions prepared in the above Examples is determined by 1) heating the various dispersions in a forced air oven at 50°C and monitoring the stability with time and 2) performing consecutive freeze-thaw cycles on the dispersions by cooling to -40°C until frozen and then allowing the dispersions to thaw at room temperature and monitoring the stability after each cycle.
  • Example 1 (b) About 270 parts of the silylated polyether prepared in Example 1 (b) above are mixed with 30 parts of a trimethylsiloxy endblocked dimethylpolysiloxane having a viscosity of 50 mm 2 /s (cs.) at 25°C for 3 hours. When the agitation ceased, the mixture immediately separates into 2 phases. About 100 parts of this heterogeneous mixture are dispersed in 200 parts of water by mixing at room temperature for 1 hour. The dispersion is unstable and immediately separates into 2 phases. Upon evaporation of the water, a heterogeneous product is obtained consisting of a friable rubber-like material and an oily liquid.
  • a textile fabric containing a mixture of polyester (Dacron) and cotton (65/35) is treated with the compositions prepared in the above Examples by dipping the fabric in aqueous dispersions containing 2 percent by weight of the various compositions prepared in the respective Examples in which the percent by weight is based on total weight of the solution.
  • the fabric is then dried for two minutes at 171°C (340°F) in a forced air oven.
  • the hand characteristics of each fabric is then rated from 1 to 5, where 5 designates a soft, silky, lubricuous hand and 1 designates a stiff, harsh, boardy hand.
  • a portion of the product is dispersed in water and an emulsion is formed which is stable after 3 months.
  • water is evaporated, a rubber-like film is formed.
  • Fabrics including polyester, cotton, wool, polyamide (nylon) and rayon are treated with the compositions of Examples 1 and 21 in accordance with the procedure described in Example 19.
  • the treated fabrics have a soft, silky, lubricuous hand.

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Claims (10)

1. Compositions de polymères siliconiques pour le traitement de matières textiles, comprenant un polyorganosiloxane à terminaisons silanoliques et un polyéther silylé de formule générale
Figure imgb0110
dans laquelle l'un au moins des R est choisi parmi le radical -NH, un radical ammonium et les radicaux
Figure imgb0111
radicaux qui sont liés au polyéther par un groupe ester, amine, amide ou ammonium, et les autres groupes R sont choisis parmi le groupe hydroxyle, des radicaux hydrocarbyloxy pouvant avoir jusqu'à 18 atomes de carbone et un radical
Figure imgb0112
R1 est un radical hydrocarboné divalent en C1 à C10 choisi parmi les groupes (―CH2)y, ―CH=CH― et un radical hydrocarboné cyclique divalent choisi parmi les groupes C6H4, C6H8, C6H10 et C10H6; A est radical silicié choisi parmi des radicaux cationiques ou anioniques de formules
Figure imgb0113
et des radicaux non ioniques de formules
Figure imgb0114
formules dans lesquelles R2 et R3, qui peuvent être indentiques ou différents l'un de l'autre, sont des radicaux hydrocarbonés monovalents C1 à C18, R4 est un radical ionique lié à un atome de silicium, formé d'atomes de carbone, d'hydrogène, d'oxygène et d'azote, choisi parmi les suivants
Figure imgb0115
Figure imgb0116
et
Figure imgb0117
R5 est un radical divalent non ionique choisi parmi R6 et un radical formé d'atomes de carbone, hydrogène, d'oxygène et d'azote, choisi parmi les suivants
Figure imgb0118
Figure imgb0119
avec la condition que si R est un radical
Figure imgb0120
R5 doit être un radical R6,
R6 est un radical en Ci à Cso choisi parmi un radical hydrocarboné divalent saturé, un radical hydrocarbyloxy divalent dont l'oxygène est en liaison éther et un radical hydrocarboné divalent insaturé, les valences insatisfaites de R6 étant liées à un atome de silicium et les valences insatisfaites de A sont satisfaites par R, et si A est un radical divalent, le rapport de A à R est 1:2, si R est cationique, A doit être anionique tandis que si R est anionique A doit être cationique, et si R est non ionique, A doit être non ionique, a est un nombre de 0 à 4, b, c et d sont chacun un nombre de 0 à 1 et la somme b + c + d doit être au moins égale à 1, et si b, c ou d est le nombre 0, R est un radical hydroxyle, hydrocarbyloxy ou un radical de formule
Figure imgb0121
e est un nombre de 0 à 2, f le nombre 0 ou 1, n le nombre 2, 3 ou 4, x un nombre au moins égal à 1 et pouvant s'élever jusqu'à 600 et y un nombre de 0 à 10.
2. Composition selon la revendication 1 dans laquelle le radical A du polyéther silylé est un radical ionique contenant du silicium, de formule ou
Figure imgb0122
Figure imgb0123
dans lesquelles R2 et R3 sont des radicaux hydrocarbonés monovalents en C1 à C18, R4 est un radical ionique lié à un atome de silicium, formé d'atomes de carbone, d'hydrogène, d'oxygène, et d'azote, choisi parmi les suivants
Figure imgb0124
Figure imgb0125
et
Figure imgb0126
 et e est un nombre de 0 à 2.
3. Composition selon la revendication 1 dans laquelle le radical A du polyéther silylé est un radical non ionique contenant du silicium et, de formule
Figure imgb0127
ou
Figure imgb0128
dans lesquelles R2 et R3 sont des radicaux hydrocarbonés monovalents C1 à C18, R5 est un radical divalent non ionique choisi parmi R6 et un radical formé d'atomes de carbone, d'hydrogène, d'oxygène et d'azote, choisi parmi les suivants
Figure imgb0129
Figure imgb0130
avec la condition que si R est un radical
Figure imgb0131
R5 doit être un radical R6,
R6 est un radical en C1 à Cso choisi parmi un radical hydrocarboné divalent saturé, un radical hydrocarbyloxy divalent dont l'oxygène est en liaison éther et un radical hydrocarboné divalent insaturé, et e est un nombre de 0 à 2.
4. Composition selon la revendication 1 dans laquelle la proportion du polyorganosiloxane à terminaisons silanoliques est de 0,25 à 99,75% en poids et celle du polyéther silylé de 99,75 à 0,25% en poids, par rapport à la somme des deux.
5. Composition selon la revendication 1 dans laquelle le polyorganosiloxane à terminaisons silanoliques est un polydiorganosiloxane à terminaisons silanoliques ayant une viscosité de 15 à 1 000 000 mm2/s (cs.) à 25°C.
6. Un procédé de préparation d'une composition pour le traitement de matières textiles, procédé selon lequel on fait réagir un polyorganosiloxane à terminaisons silanoliques avec un polyéther silylé de formule générale
Figure imgb0132
dans laquelle l'un au moins des R est choisi parmi le radical -NH, un radical ammonium et les radicaux
Figure imgb0133
 radicaux qui sont liés au polyéther par un groupe ester, amine, amide ou ammonium, et les autres groupes R sont choisis parmi le groupe hydroxyle, des radicaux hydrocarbyloxy pouvant avoir jusqu'à 18 atomes de carbone et un radical
Figure imgb0134
R1 est un radical hydrocarboné divalent en C1 à C10 choisi parmi les groupes (―CH2)y, ―CH=CH― et un radical hydrocarboné cyclique divalént choisi parmi les groupes C6H4, C6H8, C6H10, et C10H6; A est un radical silicié choisi parmi des radicaux cationiques ou anioniques de formules
Figure imgb0135
et de radicaux non ioniques de formules
Figure imgb0136
formules dans lesquelles R2 et R3, qui peuvent être identiques ou différents l'un de l'autre, sont des radicaux hydrocarbonés monovalents C1 à C18, R4 est un radical ionique lié à un atome de silicium, formé d'atomes de carbone, d'hydrogène, d'oxygène et d'azote, choisi parmi les suivants
Figure imgb0137
Figure imgb0138
et
Figure imgb0139
R5 est un radical divalent non ionique choisi parmi R6 et un radical formé d'atomes de carbone, d'hydrogène, d'oxygène et d'azote, choisi parmi les suivants.
Figure imgb0140
Figure imgb0141
avec la condition que si R est un radical
Figure imgb0142
R5 doit être un radical R6,
R6 est un radical en C1 à C50 choisi parmi un radical hydrocarboné divalent saturé, un radical hydrocarbyloxy divalent dont l'oxygène est en liaison éther et un radical hydrocarboné divalent insaturé, les valences insatisfaites de R6 étant liées à un atome de silicium et les valences insatisfaites de A sont satisfaites par R, et si A est un radical divalent, le rapport de A à R est 1:2, si R est cationique, A doit être anionique tandis que si R est anionique A doit être cationique, et si R est non ionique, A doit être non ionique, a est un nombre de 0 à 4, b, c et d sont chacun un nombre de 0 à 1 et la somme b + c + d doit être au moins égale à 1, et si b, c ou d est le nombre 0, R est un radical hydroxyle, hydrocarbyloxy ou un radical de formule
Figure imgb0143
e est le nombre de 0 à 2, f le nombre 0 ou 1, n le nombre 2, 3 ou 4, x est un nombre au moins égal à 1 et pouvant s'élever jusqu'à 600 et y un nombre de 0 à 10.
7. Procédé selon la revendication 6, dans lequel on chauffe à une température élevée le polyorganosiloxane à terminaisons silanoliques avec le polyéther silylé.
8. Composition obtenue par le procédé de la revendication 7 pour le traitement de matières textiles.
9. Un procédé de traitement de matières textiles selon lequel on recouvre le textile avec une. composition selon la revendication 1 en solution dans un diluant contenant 0,25 à 99,75 parties en poids de la composition pour 99,75 à 0,25 partie en poids du diluant, puis on durcit le textile revêtu à chaud.
10. Matière textile revêtue qui a été traitée par le procédé de la revendication 9.
EP81105625A 1980-07-18 1981-07-17 Compositions d'organopolysiloxanes pour le traitement de matières textiles; leur préparation, un procédé pour le traitement de matières textiles et matières textiles ainsi traitées Expired EP0044540B1 (fr)

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